Batch, semi-continuous or continuous hydrochlorination of glycerin with reduced volatile chlorinated hydrocarbon by-products and chloracetone levels

Abstract

The present invention relates to a process for converting a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin, by contacting the multihydroxylated-aliphatic hydrocarbon or ester thereof starting material with a source of hydrogen chloride at superatmospheric, atmospheric and subatmospheric pressure conditions for a sufficient time and at a sufficient temperature, preferably wherein such contracting step is carried out without substantial removal of water, to produce the desired chlorohydrin product; wherein the desired product or products can be made in high yield without substantial formation of undesired overchlorinated byproducts; said process carried out without a step undertaken to specifically remove volatile chlorinated hydrocarbon by-products or chloroacetone, wherein the combined concentration of volatile chlorinated hydrocarbon by-products and chloroacetone is less than 2000 ppm throughout any stage of the said process.

1. A batch, semi-batch, semi-continuous or continuous process for producing a chlorohydrin, an ester of a chlorohydrin, or a mixture thereof comprising the step of contacting glycerin, an ester of glycerin, or a mixture thereof with a source of hydrogen chloride, in the presence of a catalyst to produce a chlorohydrin, an ester of a chlorohydrin, or a mixture thereof, said process carried out without a step undertaken to specifically remove volatile chlorinated hydrocarbon by-products or chloroacetone, wherein the combined concentration of volatile chlorinated hydrocarbon by-products and chloroacetone is from about 0.01 ppm to less than 2000 ppm throughout any stage of the said process; wherein the process carried out at a hydrogen chloride partial pressure of from about 15 psia to about 1000 psia; and wherein the catalyst is selected from the group consisting of a carboxylic acid, an anhydride, an acid chloride, an ester, a lactone, a lactam, an amide, a metal organic compound, a metal salt, a compound convertible to a carboxylic acid under the reaction conditions of the process, and a combination thereof. 
     
     
       2. The process of  claim 1  wherein the combined concentration of volatile chlorinated hydrocarbon by-products and chloroacetone is from about 0.01 ppm to less than 1000 ppm throughout any stage of the said process. 
     
     
       3. The process of  claim 1  wherein the combined concentration of volatile chlorinated hydrocarbon by-products and chloroacetone is from about 0.01 ppm to less than 500 ppm throughout any stage of the said process. 
     
     
       4. The process of  claim 1  wherein the combined concentration of volatile chlorinated hydrocarbon by-products and chloroacetone is from about 0.01 ppm to less than 300 ppm throughout any stage of the said process. 
     
     
       5. The process of  claim 1  wherein the combined concentration of volatile chlorinated hydrocarbon by-products and chloroacetone is from about 0.01 ppm to less than 150 ppm throughout any stage of the said process. 
     
     
       6. The process of  claim 1  wherein the combined concentration of volatile chlorinated hydrocarbon by-products and chloroacetone is from about 0.01 ppm to less than 50 ppm throughout any stage of the said process. 
     
     
       7. The process of  claim 1  wherein the contacting step is carried out without substantial removal of water. 
     
     
       8. The process of  claim 1  wherein the chlorohydrin is dichlorohydrin. 
     
     
       9. The process of  claim 1  comprising a recycle step. 
     
     
       10. The process of  claim 1  carried out in the presence of a catalyst and a co-catalyst. 
     
     
       11. The process of  claim 1  carried out in the presence of a catalyst and a co-reactant. 
     
     
       12. The process of  claims 10  or  11  wherein the co-catalyst or co-reactant comprises a source of chloride, bromide or iodide. 
     
     
       13. The process of  claim 11  wherein the co-reactant is a non-volatile source of ionic chloride. 
     
     
       14. The process of  claim 13  wherein the co-reactant is sodium chloride. 
     
     
       15. The process of  claim 13  wherein the co-reactant is potassium chloride. 
     
     
       16. The process of  claim 13  wherein the co-reactant is a ionic liquid chloride salt. 
     
     
       17. The process of  claim 13  wherein the co-reactant is tetraalkylammonium chloride. 
     
     
       18. The process of  claim 13  wherein the co-reactant is n-butyl-methylimidazolium chloride. 
     
     
       19. The process of  claim 13  wherein the co-reactant is a polymer. 
     
     
       20. The process of  claim 19  wherein the polymer is a crosslinked divinylbenzene/styrene copolymer to which an alkylarylammonium cation is covalently linked and ion paired with chloride anion. 
     
     
       21. The process of  claim 7  wherein the hydrogen chloride source is at least 50 mole % hydrogen chloride. 
     
     
       22. The process of  claim 7  wherein the hydrogen chloride source is hydrogen chloride gas. 
     
     
       23. The process of  claim 7  wherein the chlorohydrin is a dichlorohydrin, an ester of a dichlorohydrin, or a mixture thereof. 
     
     
       24. The process of  claim 23  wherein the dichlorohydrin is 1,3-dichloropropan-2-ol; 2,3-dichloropropan-1-ol; or a mixture thereof. 
     
     
       25. The process of  claim 7  wherein the glycerin hydrocarbon is crude glycerol. 
     
     
       26. The process of  claim 25  wherein the crude glycerol contains less than 25 weight % water, and less than 25 weight % alkali or alkaline earth metal salts. 
     
     
       27. The process of  claim 7  wherein the glycerin is 1,2,3-propanetriol. 
     
     
       28. The process of  claim 7  wherein glycerin is co-fed with one or more of the following diols: 1,2-ethanediol; 1,2-propanediol, 1,3-propanediol; and butanediol positional isomers. 
     
     
       29. The process of  claim 7  wherein the catalyst is a carboxylic acid or a compound convertible to a carboxylic acid having from 1 to about 60 carbon atoms under the reaction conditions of the process. 
     
     
       30. The process of  claim 7  wherein the catalyst is a carboxylic acid or a compound convertible to a carboxylic acid having from two to about 20 carbon atoms under the reaction conditions of the process and having at least one functional group selected from the group consisting of an amine, an alcohol, a halogen, a sulfhydryl, an ether, an ester, and a combination thereof, wherein the functional group is attached no closer to the acid function than the alpha carbon wherein the catalyst is a compound convertible to a carboxylate derivative under the reaction conditions of the process. 
     
     
       31. The process of  claim 7  wherein the catalyst is selected from the group consisting of acetic acid, adipic acid, propionic acid, hexanoic acid, heptanoic acid, stearic acid, butyric acid, valeric acid, 4-methylvaleric acid, phenylacetic acid, cinnamic acid, succinic acid, polyacrylic acid, polyethylene grafted with acrylic acid, epsilon-caprolactone, delta-valerolactone, gamma-butyrolactone, epsilon-caprolactam, 6-chlorohexanoic acid, 4-hydroxyphenylacetic acids, 4-aminobutyric acid, 4-dimethylaminobutyric acid, 4-trimethylammoniumbutyric acid chloride, 4-hydroxyphenylacetic acid, 4-aminophenylacetic acid, 5-chlorovaleric acid, 5-hydroxyvaleric acid, 4-hydroxybutyric acid, 4-chlorobutyric, 5-chloropentanoic acid, and mixtures thereof. 
     
     
       32. The process of  claim 7  wherein the catalyst is selected from the group consisting of acetic acid, adipic acid, propionic acid, butyric acid, 4-methylvaleric acid, hexanoic acid, heptanoic acid, stearic acid, epsilon-caprolactone, gamma-butyrolactone, 6-chlorohexanoic acid, 4-aminobutyric acid, 4-dimethylaminobutyric acid, 4-trimethylammoniumbutyric acid chloride, 4-hydroxyphenylacetic acid, 4-aminophenylacetic acid, and mixtures thereof. 
     
     
       33. The process of  claim 7  wherein the catalyst is selected from the group consisting of acetic acid, adipic acid, epsilon caprolactone, 6-chlorohexanoic acid, delta-valerolactone, 5-chloropentanoic acid, 4-chlorobutyric acid, 4-hydroxyphenylacetic acid, 4-aminophenylacetic acid, 4-aminobutyric acid, and mixtures thereof. 
     
     
       34. The process of  claim 7  wherein the catalyst is acetic acid. 
     
     
       35. The process of  claim 7  wherein the catalyst is caprolactone. 
     
     
       36. The process of  claim 7  wherein the catalyst is an ester of glycerin, an ester of ethylene glycol or an ester of propylene glycol derived from a compound selected from the group consisting of acetic acid, adipic acid, propionic acid, hexanoic acid, heptanoic acid, stearic acid, butyric acid, valeric acid, 4-methylvaleric acid, phenylacetic acid, cinnamic acid, succinic acid, benzoic acid, polyacrylic acid, polyethylene grafted with acrylic acid, epsilon caprolactone, delta-valerolactone, gamma-butyrolactone, epsilon-caprolactam, 6-chlorohexanoic acid, 4-hydroxyphenylacetic acids, 4-aminobutyric acid, 4-dimethylaminobutyric acid, 4-trimethylammoniumbutyric acid chloride, 4-hydroxyphenylacetic acid, 4-aminophenylacetic acid, 5-chlorovaleric acid, 5-hydroxyvaleric acid, 4-hydroxybutyric acid, 4-chlorobutyric, 5-chloropentanoic acid, and mixtures thereof. 
     
     
       37. The process of  claim 7  wherein the catalyst is an ester selected from the group consisting of glycerin monoacetate, glycerin diacetate, glycerin distearate, 1-chloro-2,3-propanediolmonoacetate, a glycerin ester of a polycarboxylic acid, and mixtures thereof. 
     
     
       38. The process of  claim 7  wherein the catalyst is an insoluble polymer containing carboxylic acid moieties or esters thereof. 
     
     
       39. The process of  claim 38  wherein the insoluble polymer or copolymer is a polyester, polyacrylic acid, polyamide, polyacrylate and copolymers thereof and mixtures thereof. 
     
     
       40. The process of  claim 7  wherein the catalyst has a vapor pressure lower than the chlorohydrin or its azeotrope with water. 
     
     
       41. The process of  claim 1  which is carried out at a hydrogen chloride partial pressure of from about 35 psia to about 600 psia. 
     
     
       42. The process of  claim 1  which is carried out at a hydrogen chloride partial pressure of from about 55 psia to about 150 psia. 
     
     
       43. The process of  claim 1  which is carried out at a hydrogen chloride partial pressure of from about 20 psia to about 120 psia. 
     
     
       44. The process of  claim 1  which is carried out at a temperature of from about 25° C. to about 300° C. 
     
     
       45. The process of  claim 1  which is carried out at a temperature of from about 25° C. to about 200° C. 
     
     
       46. The process of  claim 1  which is carried out at a temperature of from about 30° C. to about 160° C. 
     
     
       47. The process of  claim 1  which is carried out at a temperature of from about 40° C. to about 150° C. 
     
     
       48. The process of  claim 1  which is carried out at a temperature of from about 50° C. to about 140° C. 
     
     
       49. The process of  claim 1  wherein glycerin source is derived from an oleochemical or biomass. 
     
     
       50. The process of  claim 1  wherein the glycerol source is a mixture of synthetic glycerol biomass-derived glycerol. 
     
     
       51. The process of  claim 29  wherein the catalyst is represented by Formula (a) as follows: 
       
         
           
           
               
               
           
         
       
       wherein R′ is selected from an amine, an alcohol, a halogen, a sulfhydryl, and an ether; and an alkyl, an aryl, and an alkaryl group of from 1 to about 20 carbon atoms having a group selected from an amine, an alcohol, a halogen, a sulfhydryl, and an ether; and a combination thereof; and wherein R is selected from a hydrogen, an alkali, an alkali earth, a transition metal; and an alkyl, an aryl, and an alkaryl group of from 1 to about 20 carbon atoms having R′; or a combination thereof; and wherein R is selected from a hydrogen, an alkali, an alkali earth or a transition metal or an alkyl, an aryl or an alkaryl group of from 1 to about 20 carbon atoms. 
     
     
       52. The process of  claim 51  wherein the catalyst is selected from the group consisting of lactones, esters, lactams, amides and functionalized carboxylic acids. 
     
     
       53. The process of  claim 51  wherein the catalyst is selected from the group consisting of a caprolactone, a carboxylic acid amide, a carboxylic acid lactone, a caprolactam, and combinations thereof. 
     
     
       54. The process of  claim 51  wherein the catalyst is selected from the group consisting of 6-hydroxyhexanoic acid, 6-chlorohexanoic acid, caprolactone, ε-caprolactam, and γ-butyrolactam; γ-butyrolactone, δ-valerolactone, and ε-caprolactone; 6-aminocaproic acid; 4-aminophenylacetic acid, 4-aminobutyric acid, 4-dimethylaminobutyric acid, 4-hydroxyphenylacetic acid, 4-dimethylaminophenylacetic acid, aminophenylacetic acid, lactic acid, glycolic acid, 4-dimethylaminobutyric acid, 4-trimethylammoniumbutyric acid, and combinations thereof. 
     
     
       55. The composition of  claim 1  wherein at least some of the chlorohydrin is a dichlorohydrin. 
     
     
       56. The composition of  claim 55  wherein the dichlorohydrin is 1,3-dichloro-2-propanol or 2,3-dichloro-1-propanol. 
     
     
       57. The process of  claim 1  wherein the volatile chlorinated hydrocarbon by-products comprise 1,2,3-trichloropropane and isomers thereof, 1,3-dichloropropene, 1,2-dichloropropene, 2,3-dichloro-1-propene, 2-chloro-2-propene-1-ol, 3-chloro-propene-1-ol; isomers thereof; or mixtures thereof.